Method for reacting organic halides

ABSTRACT

A method for carrying out reactions of the Friedel-Crafts type, such as alkylation, acylation, polymerization, sulfonylation and dehydrohalogenation. The reactions are catalyzed by arene-metal tricarbonyl complexes and when the reaction vessel contains aromatic substrates the catalyst may be generated in situ from a metallic hexacarbonyl. The arene-metal tricarbonyl catalyst is more selective than conventionally employed Friedel-Craft catalysts in that it yields generally para isomers with little of the ortho variety and very little if any of the meta variety when the aromatic substrate is reacted with organic halide. It is also possible to form the arene-metal tricarbonyl catlyst outside of the reaction vessel and then proceed by adding it to the vessel containing the substrate and the organic halide as is the case with dehydrohalogenation reactions wherein there are no aromatic rings available, the substrate in that instance being aliphatic.

United States Patent [1 1 Farona et a1.

[ METHOD FOR REACTING ORGANIC HALIDES [75] lnventors: Michael F. Farona,Cuyahoga Falls;

James F. White, Akron, both of Ohio [73] Assignee: The University ofAkron, Akron,

Ohio

[22] Filed: Apr. 10, 1974 [21] Appl. No.: 459,481

Related US. Application Data [60] Division of Ser. No. 339,637, March 9,1973, Pat.

No. 3,832,403, which is a continuation-in-part of Ser. No. 119,908,March 1, 1971, abandoned.

[52] US. Cl 260/2 H; 260/2 R; 260/469; 260/578; 260/591; 260/592;260/590;

260/613 R; 260/613 D; 260/619 R; 260/620; 260/668 B; 260/671 B Natta,G., et al., "Chromium Carbonyl Complexes with Polystyrene, Chem. Abst.,Vol. 66; entry 95,607c, p. 8979, (1967).

[ 1 Dec. 16, 1975 Cais, M., et a1., Organometallic Studies, XXIV," Chem.Abst., Vol. 69, entry 43368t, p. 4056, (1968). Karapinka, (3.,(Arene)tricarbonylchromium Catalyst for the Polymerization of Ethylene,Chem. Abst., Vol. 73, entry 67029s, p. 9, (1970).

Primary Examiner-Wilbert .l. Briggs, Sr. Attorney, Agent, orFirml-lamilton, Renner & Kenner [57] ABSTRACT A method for carrying outreactions of the Friedel- Crafts type, such as alkylation, acylation,polymerization, sulfonylation and dehydrohalogenation. The reactions arecatalyzed by arene-metal tricarbonyl complexes and when the reactionvessel contains aromatic substrates the catalyst may be generated insitu from a metallic hexacarbonyl. The arene-metal tricarbonyl catalystis more selective than conventionally employed Friedel-Craft catalystsin that it yields generally para isomers with little of the orthovariety and very little if any of the meta variety when the aromaticsubstrate is reacted with organic halide. It is also possible to formthe arene-metal tricarbonyl catlyst outside of the reaction vessel andthen proceed by adding it to the vessel containing the substrate and theorganic halide as is the case with dehydrohalogenation reactions whereinthere are no aromatic rings available, the substrate in that instancebeing aliphatic.

8 Claims, No Drawings METHOD FOR REACTING ORGANIC HALIDES CROSSREFERENCE TO RELATED APPLICATION This application is a divisionalapplication of U.S. Ser. No. 339,637, now U.S. Pat. No. 3,832,403, whichis in turn a continuation-in-part application of U.S. Ser. No. 119,908,filed Mar. 1, 1971, now abandoned.

BACKGROUND OF THE INVENTION Substitution of halogens from organiccompounds by other organic groups or the mere removal of halogens,without substitution, to form new organic compounds is well known by avariety of standard name reactions. The Friedel-Crafts type ofreactions, usually carried out by the catalyst aluminum trichloride, arean example.

The reactivity of the arene-metal tricarbonyl complexes has also beenexamined and it is known that the tricarbonylc hlorobenzenechromiumcomplex will enter into a nucleophilic reaction with methyl alcohol toform the anisole complex. Further, electrophilic reactions are alsofacilitated such as Friedel-Crafts acetylation of thetricarbonyl-benzene chromium complex with acetyl chloride in thepresence of aluminum trichloride. Both types of reaction yield a productwhich retains the arene-metal tricarbonyl complex.

SUMMARY OF THE INVENTION It is therefore an object of the presentinvention to provide a method for reacting organic halides inalkylations, acylations, polymerizations, sulfonylations anddehydrohalogenations.

It is another object of the present invention to provide a method forcarrying out these reactions in the presence of an arene-metaltricarbonyl catalyst.

It is a further object of the present invention to employ a catalystwhich is easier to use, with respect to storage and handling, in thatthe catalyst may be generated in solution within the reaction vessel orwithout the reaction vessel and subsequently added thereto.

It is yet another object of the present invention to employ a catalystwhich promotes attack on the aromatic ring generally at the paraposition rather than at the ortho position and usually excludes attackat the meta position.

These and other objects of the invention, and the advantages thereof,will be apparent in view of the detailed disclosure of the invention asset forth below.

In general, it has now been found that an organic halide RX, and anarene-metal tricarbonyl represented by the general formula,

will react to form a carbonium ion RQ It was further found that thehighly reactive carbonium ion will release a hydrogen ion, or react insitu and in a repetitive process with the original organic halide orwith other organic compounds present within the reaction vessel. Manydifferent classes of products may be formed by predetermined selectionof the appropriate organic reactants.

DESCRIPTION OF THE PREFERRED EMBODIMENTS M(CO) 3 where R is selectedfrom the class consisting of electron donating and ring activatinggroups such as hydrogen, alkyl groups having from one to about sixcarbon atoms, alkoxide groups having from one to about four carbonatoms, aryl and aryloxide groups having from six to about 12 carbonatoms including alkyl substituents, amino and hydroxide. The metal, M,is selected from the group consisting of Cr, Mo, and W with molybdenumbeing preferred.

Representative alkyl groups include methyl, ethyl, isopropyl, t-butyl,pentyl, hexamethyl and the like. Representative alkoxide groups includemethoxy, ethoxy, propoxy, butoxy, sec-butoxy and the like.

Representative aryl groups include phenyl, naphthyl and the phenyl ringwith substituted alkyl groups such as methyl, ethyl, propyl, butyl,sec-butyl, pentyl, 2-pentyl, hexamethyl and the like. A representativearyloxide is diphenyl ether.

R' may further be selected from the class consisting of ringdeactivating and electron withdrawing groups such as the halides, thehaloalkyls, the alkylbenzoate esters, the aldehydes and sulfonylhalides, particularly sulfonyl chloride. Representative halides arefluoro. chloro and bromo, and representative alkylbenzoate esters arethose having from one to three carbon atoms such as methyl benzoate,ethyl benzoate, propyl benzoate and isopropyl benzoate. Representativealdehydes are those having from one to four carbon atoms. Representativehaloalkyl groups include methyl bromide, methyl chloride and methylfluoride.

In addition to the aforementioned mono-substituted phenyl compoundswhich may be utilized it is also possible to select poly-substitutedphenyl compounds having up to five substituent groups. The genericformula for such a compound may be expressed as follows:

a R R' F (3) wherein R may be the same as any of the aforementioned Rgroups including hydrogen. As will be obvious to one skilled in the art,a large number of the existing poly-substituted phenyl compounds canthus be used in accordance with the teaching of this pioneer invention.Since it would be impractical to provide an all inclusive listing, onlysome of the representative compounds according to formula F(3) will beset forth.

Representative compounds wherein one or more of the R' groups are otherthan hydrogen include anisole, chlorobenzene, benzyl chloride, benzylfluoride, phenol, toluene, t-butyl benzene, o,m and p-dichlorobenzene,dipbenyl ether, biphe nyl, o,m and p-xylene, p-toluene sulfonylchloride, methyl benzoate, ethyl benzoate, propyl benzoate, isopropylbenzoate, 2,3-dimethoxyaniline, 2,4-dihydroxytoluene,3,4-dimethoxytoluene, 4-hydroxy-3-methoxytoluene, l,2,4,5-tetrameth- 3ylbenzene, 3,4,5-trihydroxytoluene and l,3-dihydroxy-4,5,6-trimethylbenzene.

Selection of any specific aromatic compound will of course be dependentupon factors such as the product desired and the availability orexistence of the compound. A person skilled in the art will generallyknow numerous existing compounds. Moreover, as to other compounds, anystandard reference book, such as the CRC Handbook of Chemistry andPhysics, could be consulted thus enabling the skilled artisan to obtainreadily the names of other existing compounds.

Preparation of the catalyst according to F(2) is necessarily precedentto a catalysis reaction when phenyl radicals are neither present norconstituents of the reactants chosen to form the product compounds.Thus, in the case of dehydrohalogenation reactions, the catalyst willpromote the formation of the olefin, but it must be prepared in advanceas there are no aromatic rings available in the reaction vessel.

Thus, a utility of the present invention is that this catalyst may begenerated during the catalysis reaction. Thus, when the metalhexacarbonyl and a substrate reactant having a phenyl radicalconstituent are brought together in a reaction vessel, the arene-metaltricarbonyl catalyst will be generated in situ. Upon the addition of thedesired organic halide, the particular reaction, e.g., alkylation,acylation, polymerization, sulfonylation, will then proceed to form thedesired products.

According to the method of the present invention, aromatic substratesare combined with organic halides, having the generic formula RX, in thereaction vessel. The catalyst removes the halogen forming a highlyreactive carbonium ion on the organic moiety R. Subsequent attack by thecarbo nium ion upon the substrate yields a product, resulting from theattachment of the organic radical R to the substrate, and a hydrogenion. The hydrogen ion quickly removes the halogen with at least partialregeneration of the catalyst. In this manner alkylations, acylations,polymerizations and sulfonylations occur. Of course, the catalyst alsopromotes dehydrohalogenation. However, since there is no aromaticsubstrate the catalyst merely removes the halogen from the organichalide to yield an olefin.

The organic halide RX, wherein X is generally selected from bromine,chlorine and fluorine, will be chosen according to the desired reaction,e.g., alkyl, aryl or acyl halides for alkylation and acylation, sulfonylhalides for sulfonylation and polymerization and M (CO) 6 Step 2 alkylhalides for dehydrohalogenation. The organo group, or R. may thereforebe selected from the class consisting of alkyl radicals having from oneto about 20 carbon atoms and alkyl substituted phenyl radicals havingfrom seven to about l2 carbon atoms. Alkoxide radicals having from oneto about four carbon atoms and aldehydes having from one to about fourcarbon atoms, and haloalkyl groups such as methyl bromide, methylchloride and methyl fluoride may also be used in the copolymerizationreaction. Substituted phenyl and napthyl radicals are preferred tophenyl radicals for the alkylation and polymerization reactionsutilizing an aromatic halide inasmuch as the catalyst removes, forinstance, chlorine much more readily from benzyl chloride than fromchlorobenzene.

Representative alkyl groups include methyl, ethyl, propyl, butyl,pentyl, hexyl, heptyl, octyl, nonyl, decyl isomers thereof and the like.Representative substituted phenyl radicals include tolyl, xylyl, methylnaphthyl and the like. Furthermore, when selecting the xylenes, dihalocompounds may be utilized as the catalyst can readily remove bothhalogens from their methyl partner. As before, the skilled artisan canrefer to a reference handbook to ascertain the existing organic halideswhich he may desire to react.

Whether the catalyst is prepared within the reaction vessel by reactingmolybdenum hexacarbonyl with the aromatic substrate, or it is separatelyprepared and added, the reactants are all placed within the reactionvessel. Generally, the reactants are soluble within the substrate;however, if such is not the case, the reaction may be carried out inheptane or any other saturated liquid hydrocarbon or any aryl such asbenzene or substituted benzene. The reaction is preferably carried outin an inert atmosphere such as nitrogen. In order to generally initiatethe reaction, the vessel is usually fitted with a reflux condenser andheated from ambient temperatures through a temperature range of a fewdegrees to approximately C, depending upon the type of reaction and thereactants. Reaction time is also dependent upon the latter factors andaccordingly ranges from about one hour to about thirty six hours orlonger. During this time it is necessary to keep the reactants mixedwhich may be readily accomplished with a conventional magnetic stirreror the like. Mechanisms for the various reactions are as follows:

An alkylation according to the present invention is thought to proceedaccording to the following reaction mechanism;

A 3C0 l -continued Step 4 RI RI H R' ax @242 R M R R' X-M (CO) 3 M (CO)3 where R is an alkyl or alkyl substituted phenyl group as noted above Ris hydrogen, alkyl, alkoxide, sulfonyl chloride,

hydroxide, aryl or aryl oxide as noted above M is a metal from thegroup, Cr, Mo and W, and X is a halogen from the group of Br, Cl and F.The catalyst is formed in the reaction vessel from part of the aromaticsubstrate reactant or it may be added in its active form whereby Step 1is omitted. in Step 2, it proceeds to remove the halogen from theorganic halide, RX, resulting in the formation of a highly reactivecarbonium ion, R", which subsequently attacks the remaining part of thearomatic substrate, as in Step 3, with concurrent release of a hydrogenion. In Step 4, the hydrogen ion removes the halogen and the catalyst isregenerated.

An acylation according to the present invention is thought to proceedaccording to the following reaction mechanism;

M is a metal from the group Cr, Mo and W, and

X is a halogen from the group of Br, Cl and F. The catalyst is againformed in Step I, as described before or merely added directly to thereactants. In

Step 2 it proceeds to remove the halogen from the organic acid halideresulting in the formation of a highly reactive acyl cation RC*=O, whichsubsequently attacks the aromatic substrate reactant, as in Step 3, withconcurrent release of a hydrogen ion. In Step 4,

the hydrogen ion removes the halogen and the catalyst is regenerated.

Two types of polymers may be produced according to the presentinvention. A branched structure may be formed by the polymerization ofone monomeric substance or the combination of two monomers. A linearpolymer may be produced by selecting an aryl substrate, A, having onlytwo positions subject to carbonium ion attack and having ligands at eachof the other positions relatively unsusceptible to carbonium ion attack.The organic halide selected, B, is a dihalo-com- R is an alkyl or alkylsubstituted phenyl group as noted above R is hydrogen, alkyl, alkoxideor hydroxide, aryl or aryloxide as noted above of the molecule, thusforming a linear polymerization of the type AB.

Polymerization to form a branched polymer according to the presentinvention is thought to proceed according to the following reactionmechanism;

R is an aryl radical as noted above R is alkyl, alkoxide, or haloalkylas hoted above,

M is a metal from the group Cr, Mo and W, and

X is a halogen from the group of Br, Cl and F. The organic halide has anaryl ring, and therefore will react with molybdenum hexacarbonyl as inStep 1, or if desired, the active form of the catalyst may be preparedseparately and added to the monomeric halide R- RX as in Step 2 wherethe halogen is removed resulting in the formation of a highly reactivecarbonium ion, R-R, which subsequently attacks the organic halide as inStep 3, with concurrent release of a hydro- Step 1 gen ion. The catalystis again regenerated as by Step 4.

The reaction generally proceeds with substantial conversion of themonomer to the dimer RR'R-- R'X; then loss of the halogen again resultsin the carbonium ion which combines in a repetitive process to produce apolymer having an average number molecular weight ranging fromapproximately 5,000 to 30,000. Owing to the reactive sites of a phenylring, 0, m,' and p, to the ligand R, the polymer is highly branchedPolymerization to form a linear copolymer according to the presentinvention is thought to proceed according to the following reactionmechanism:

+ other products H where R is alkyl, alkoxide, or hydroxide as notedabove R is alkyl, alkoxide, aldehyde, sulfonyl or haloalkyl as notedabove,

M is a metal from the group Cr, Mo and W, and

X is a halogen from the group of Br, Cl and F.

Removal of both halides from the dihalo-compound produces two reactivecarbonium ions which will combine with the available positions of thearomatic substrate compound in a repetitive process to form a linearcopolymer of average number molecular weight ranging between 5.000 and30:000

A sulfonylation according to the present invention is thought to proceedaccording to the following reaction mechanism:

M is a metal from the group Cr. Mo and W. and X is a halogen from thegroup of Br, Cl and F. The

A dehydrohalogenation according to the present invention is thought toproceed according to the following reaction mechanism:

R is an alkyl or alkyl substituted phenyl group as noted above R ishydrogen. alkyl, alkoxide, aryl, aryloxide or hydroxide as noted above Ris an alkyl group as noted above R! is hydrogen, alkyl, alkoxide,sulfonyl chloride, amino, aryl and aryloxide, halide, hydroxide andalkylbenzoate esters as noted above M is a metal from the group Cr, Moand W. and

X is a halogen from the group of Br, Cl and F. In this reaction it isdesirable to form the active catalyst apart from the reactants sinceM(CO) will not combine with an alkyl halide and if an aryl halide ispresent some alkylation will occur. in Step 1. the catalyst removes thehalogen from the alkyl halide. R-X. resulting in the formation of ahighly reactive carbonium ion. R. With subsequent loss of a hydrogenion. as in Step 2, an alkene product is formed. in Step 3, the hydrogenion removes the halogen and the catalyst is regenerated.

The invention will be more fully understood by reference to thefollowing examples which describe the various types of reactions.

EXAMPLE I An alkylation by an organic halide of an aryl compound ispromoted by the combination of I22 gms. of phenol; 20 cc. of t-butylchloride; and 50 mg. of molybdenum hexacarbonyl in 120 cc. of thesolvent heptane. These reactants are placed in a suitable vessel andmixed as by a magnetic stirring apparatus. The vessel is fitted with areflux condenser and is then heated, to approximately 98C. for l8 to 24hours. At the end of this time period, the desired product is separatedby suitable means well known to one skilled in the art.

EXAMPLE [I An acylation by an acid halide of an aryl compound ispromoted by the combination of I25 cc. of anisole; 4 cc. of acetylchloride and 25-50 mg. of molybdenum hexacarbonyl. These reactants areplaced in a suitable vessel. and thoroughly mixed while refluxing atapproximately 100C. for 36 hours. At the end of this time period. thedesired product is separated by suitable means.

EXAMPLE ill A polymerization of an organic halide to form a branchedpolymer is promoted by the combination of I gms. of benzyl chloride with50 mg. of molybdenum hexacarbonyl. The compounds are placed in asuitable vessel. mixed and refluxed at approximately l()()C. for 1 hour.At the end of this time period, the branched polymer is separated bysuitable means.

12 EXAMPLE IV A linear polymer may be formed by combining 7.3 gms. ofa.adichloro-p-xylene; 5.4 gms. of durene, and 10 mg. of molybdenumhexacarbonyl in 100 cc. of the solvent. decalin. The reactants areplaced in a suitable vessel. mixed and refluxed at approximately ll C.for 3 hours. At the end of this time period the linear polymer isseparated by suitable means.

EXAMPLE V A sulfonylation of an aryl sulfonyl halide is promoted bycombining 160 cc. of toluene; 3.8 gms. of p-tosyl chloride and 25 to mg.of molybdenum hexacarbonyl in a suitable vessel. The reactants are thenmixed and refluxed at approximately I l0C. for 36 hours. At the end ofthis time period, the desired product is separated by suitable means.

EXAMPLE V] A dehydrohalogenation of an organic halide is promoted by thecombination of cc. of t-butyl chloride with 200 mg. of toluenemolybdenum tricarbonyl. The compounds are placed in a suitable vessel,mixed and refluxed at approximately 51C. for 4 hours. At the end of thistime period the desired product is separated by suitable means.

The results of these and similar reactions have been set forth in Tablesl-5 below. In Table l, examples l-lO represent alkylations. In Table 2.examples l-6 represent acylations. In Table 3, example 1 representsformation of a linear polymer and examples 2-3 represent formation ofbranched polymers and 4-5 represent branched or linear polymers. inTable 4. examples 1-3 represent sulfonylations. In Table 5, example l, adehydrohalogenation reaction was attempted without the arene metaltricarbonyl catalyst and no reaction was evidenced. in example 2. thecatalyst was present, being first prepared as in H2) above, and thealkene, isobutylene, was quickly formed thereby. Although the productmay be isolated, by continuing the reaction. the polymeric productswhich are known to occur when isobutyl cations attack isobutylene areprepared.

Thus, it can be seen that the disclosed invention carries out theobjects of the invention set forth above. As will be apparent to thoseskilled in the art, many modifications can be made without departingfrom the spirit of the invention herein disclosed and described, thescope of the invention being limited solely by the scope of the attachedclaims.

Table l Alkylation Reactions Arom utic Organic Added Reaction SubstrateHalide Catalyst Conditions Yield Comments I. Toluene Lbutyl chlorideMolCO) Reflux 17.9 g Exclusivelv para (100 ml) (12.6 g) (0.21) g) 5 hr38% substitution 2. Toluene t-but \l chloride TolMo(COl;, Reflux I67 g(ml) ml) (llbgl (().2llg| l hr 81.87:

3. Toluene Cyclohexyl MolCO 1.; Reflux 19.7 g (loll mll chloride [(1 g)(0.05 g) 6 hr 84.5%

4. Toluene Benzyl MMCOI Reflux 16.4 g 100% alkvlation. I07:

[200 ml] chloride (I211 gl (0.03 g) 12 hr 91]?! polymer. 909E totvlphenlmethane 5. Toluene n-propyl chloride TolMo(COl; 7.8 g Carried out inglass- (5ll ml) (89 g) [0.20 g) 6 hr 505% lined Parr bomb. productexclusively p-cmene 6. t-hutyl n-chloroheptane MotCOh. l40 Onl\'second-an benzene (8.8 g] (0.0! g) 24 hr alltvlutes obtained (55 ml) 7.Toluene Cyclohexyl TQIMMCOL, Reflux l .8 g

Table l-continued Alkylation Reactions Aromatic Organic Added ReactionSubstrate Halide Catalyst Conditions Yield Comments ml) fluoride (11.2g) (0.1 g) 6 hr 67.3% 8. Toluene Cyclohexyl TolMotCOl Reflux 6.7 gExtensive catalyst ml) bromide (26.4 g) (0.1 g) 8 hr 23.491decomposition 9. Anisole t-but l chloride Mo(CO) 135 g (150 ml) 6.8 g)0.03 g 24 hr 79% 10. Phenol t-butyl chloride Mo(CO).. Reflux 18.8 g mlheptane solvent.

(12.0 g] (0.01 g) 18 hr 96% 93% pt-but vlphenol. 3%

2.6-di-t-butylphenol Table 2 Acylation Reactions Aromatic Organic AddedReaction Substrate Halide Catalyst Conditions Yield Comments 1. TouleneAcetyl Mo(COJ.. Reflux 1.2 g Only pmethy1 aceto- (100 ml) chloride (7.8g) (0.15 g] 24 hr 9% phenone isolated 2. Toulene Propionyl Mo(COl..Reflux 1.85 g Only para acylation 160 ml) chloride 6.35 g) (0.05 g) 24hr 18% obtained 3. Toluene Benzoyl chloride Mo(CO]. Reflux 2.5 g Onlyp-methyl (160 ml) 6.05 g] (0.15 g) 18 hr 297% benzophenone isolated 4.Toluene Benzoyl chloride TolMo(CO);, Reflux 5.65 g Same product as 3(160ml) 6.05 g) (0.02 g) 12 hr 67% 5. Anisole Acetyl chloride Mo(COl 10010.2 g 90% p-methoxyacetoml) 7.8 g) (0.02 g) 36 hr 68% phenone. 4%o-methoxyacetophenone 6. Anisole Benzoyl chloride TolMo[CO);, 100 74 gOnly p-methoxybenzoml) (7.0 g (0.15 g) 18 hr 70'7r phenone isolatedTable 3 Polymerization Reactions Aromatic Organic Added ReactionSubstrate Halide Catalyst Conditions Yield Comments 1. Durenep-xylylene- M0(CO) 1 10 9.6 g Copolymer nearly insoluble dichloride 0.01g 3 hr (98%) in common organic solvents 2. Benzyl MO(CO]|$ 1 10 100%chloride (0.1 g) 1 hr (neat) 3. Benzyl TolMo(CO)=1 140 100% fluoride(neat) 4. Diphenyl Benzene-1.3-di- Mo(CO) 1 10 1.4 g Tan-coloredcopolymer ether sulfonylchloride (0.1 g) 3 hr 22% (2.6 g [4.3 g) 5.Diphenyl Benzene-1.3-di- TolM0(CO); 1 10" 2.1 g Same as 4.

ether sulfonylchloride (0.1 g] 3 hr 32% (2.6 g) (4.3 g)

Table 4 Sulfonylation Reactions Aromatic Organic Added ReactionSubstrate Halide Catalyst Conditions Yield Comments 1. Toluene Tosylchloride Mo(CO]. Reflux 2.1 g Product is 4.4-

ml) (3.8 g] (0.02 g] 36 hr 439? ditolylsulfone 2. Anisole Tosyl chlorideMo(COl. 135 1.15 g Product is 4-methyl- 160 ml) (3.8 g) (0.02 g) 24 hr22% 4-methoxydiphen lsulfone 3. Anisole Tosyl chloride TolMolCO )1, 1 151.3 g Same as 2 (160 ml) (3.8 g) (0.03 g) 18 hr 25% Table 5Dehydrohalogenation Reaction Aromatic Organic Added Reaction SubstrateHalide Catalyst Conditions Yield Comments 1. t-butyl chloride Mo(CO)..reflux. 20 hr. none no reaction. 96% Mo(CO),

recovered 2. t-butyl chloride Toluenereflux. 4 hr. large amounts of HCIevolved.

( 100 ml) Mo(CO); 2 polymeric substances obtained What is claimed is:

l. The polymerization of an aromatic substrate monomer to form abranched polymer comprising the steps of: charging a reaction vesselwith a metallic hexacarbonyl compound having the general formula M(CO).;where M is selected from the group consisting of Cr, Mo and W, addingaromatic substrate monomers having the general formula R(R'-X),, whereinR is an aryl radical and R' is selected from the group consisting ofalkyl groups having from one to about six carbon atoms, alkoxide groupshaving from one to about four carbon atoms, and haloalkyl, and X isselected from the group consisting of bromine. chlorine and fluorine,and n is an integer from 1 to 5, reacting said metallic hexacarbonylcompound with part of said aromatic substrate monomer to yield an arenemetal tricarbonyl catalyst having the general formula heating saidreaction vessel from ambient temperatures to a temperature sufficient tocause said catalyst to polymerize said aromatic substrate monomers byremoving the halide from said aromatic substrate monomers to form activearomatic substrate monomers having a carbonium ion which said activemonomers initiate and continue said polymerization to form the branchedpolymers.

2. The process as in claim I, wherein said carbonium ion is formed in atemperature range from a few degrees above said ambient temperature toabout 135C.

3. The process as in claim I, wherein said reaction is carried out in aninert atmosphere.

4. The process as in claim 3, wherein said inert atmosphere is nitrogen.

5. The process as in claim I, wherein said reaction is carried out in asolvent selected from the group consisting of a saturated liquidhydrocarbon and liquid aryl compounds.

6. The process as in claim 1, wherein said aromatic substrate isselected from the group consisting of benzyl chloride and benzylfluoride.

7. The process as in claim I, wherein the metal of said arene metaltricarbonyl catalyst is molybdenum and where the R' constituent of saidcatalyst is a methyl radical.

8. The process of polymerizing an aromatic substrate monomer in thepresence of an arene metal tricarbonyl catalyst to form a branchedpolymer comprising the steps of: Charging a reaction vessel with anaromatic substrate monomer having the general formula R(- R'X),, whereinR is an aryl radical, R is selected from the group consisting of alkylgroups having from one to about six carbon atoms, alkoxide groups havingfrom one to about four carbon atoms and haloalkyl, and X is selectedfrom the group consisting of bromine, chlorine and fluorine, and n is aninteger from one to five. adding an arene metal tricarbonyl catalysthaving the general formula wherein R is an aryl radical and wherein R isselected from the group consisting of hydrogen, alkyl groups having fromone to about six carbon atoms, alkoxide groups having from one to aboutfour carbon atoms, aryl and aryloxide groups having from six to abouttwelve carbon atoms including alkyl substituents, amino, halide, alkylbenzoate esters having from one to three carbon atoms, sulfonyl chlorideand hydroxide, and M is selected from the group consisting of Cr, Mo,and W. and n is an integer from I to 5. heating said reaction vesselfrom ambient temperatures to a temperature sufficient to cause saidcatalyst to polymerize said aromatic substrate monomers by removing thehal-ide from said aromatic substrate monomers to form active aromaticsubstrate monomers having a carbonium ion which said active monomersinitiate and continue said polymerization to form branched polymers.

1. THE POLYMERIZATION OF AN AROMATIC SUBSTRATE MONOMER TO FORM ABRANCHED POLYMER COMPRISING THE STEPS OF: CHARGING A REACTION VESSELWITH A METALLIC HEXACARBONYL COMPOUND HAVING THE GENERAL FORMULA M(CO)6WHERE M IS SELECTED FROM THE GROUP CONSISTING OF CR, MO AND W, ADDINGAROMATIC SUBSTRATE MONOMERS HAVING THE GENERAL FORMULA R-(R''-X)NWHEREIN R IS AN ARYL RADICAL AND R'' IS SELECTED FROM THE GROUPCONSISTING OF ALKYL GROUPS HAVING FROM ONE TO ABOUT SIX CARBON ATOMS,ALKOXIDE GROUPS HAVING FROM ONE TO ABOUT FOUR CARBON ATOMS, ANDHALOALKYL, AND X IS SELECTED FROM THE GROUP CONSISTING OF BROMINE,CHLORINE AND FLUORINE, AND N IS AN INTEGER FROM 1 TO 5, REACTING SAIDMETALLIC HEXACARBONYL COMPOUND WITH PART OF SAID AROMATIC SUBSTRATEMONOMER TO YIELD AN ARENE METAL TRICARBONYL CATALYST HAVING THE GENERALFORMULA
 2. The process as in claim 1, wherein said carbonium ion isformed in a temperature range from a few degrees above said ambienttemperature to about 135*C.
 3. The process as in claim 1, wherein saidreaction is carried out in an inert atmosphere.
 4. The process as inclaim 3, wherein said inert atmosphere is nitrogen.
 5. The process as inclaim 1, wherein said reaction is carried out in a solvent selected fromthe group consisting of a saturated liquid hydrocarbon and liquid arylcompounds.
 6. The process as in claim 1, wherein said aromatic substrateis selected from the group consisting of benzyl chloride and benzylfluoride.
 7. The process as in claim 1, wherein the metal of said arenemetal tricarbonyl catalyst is molybdenum and where the R'' constituentof said catalyst is a methyl radical.
 8. The process of polymerizing anaromatic substrate monomer in the presence of an arene metal tricarbonylcatalyst to form a branched polymer comprising the steps of: charging areaction vessel with an aromatic substrate monomer having the generalformula R-(R''-X)n wherein R is an aryl radical, R'' is selected fromthe group consisting of alkyl groups having from one to about six carbonatoms, alkoxide groups having from one to about four carbon atoms andhaloalkyl, and X is selected from the group consisting of bromine,chlorine and fluorine, and n is an integer from one to five, adding anarene metal tricarbonyl catalyst having the general formula